View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by JRC Publications Repository Effect of the nature and concentration of phthalates on their migration from PVC materials under dynamic simulated conditions of mouthing C. Simoneau and P. Hannaert D. Sarigiannis, ed. EUR 23813 EN 1 The mission of the IHCP is to provide scientific support to the development and implementation of EU policies related to health and consumer protection. The IHCP carries out research to improve the understanding of potential health risks posed by chemical, physical and biological agents from various sources to which consumers are exposed. European Commission Joint Research Centre Institute for Health and Consumer Protection Contact information Address: DG JRC, IHCP TP 260, I-21020 Ispra E-mail: [email protected] Tel.: 39.0332.785889 Fax: 39.0332.785707 http://ihcp.jrc.ec.europa.eu/ http://www.jrc.ec.europa.eu/ Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication. Europe Direct is a service to help you find answers to your questions about the European Union Freephone number (*): 00 800 6 7 8 9 10 11 (*) Certain mobile telephone operators do not allow access to 00 800 numbers or these calls may be billed. A great deal of additional information on the European Union is available on the Internet. It can be accessed through the Europa server http://europa.eu/ JRC 51604 EUR 23813 EN ISBN 978-92-79-12260-6 ISSN 1018-5593 Luxembourg: Office for Official Publications of the European Communities OPOCE © European Communities, 2009 Reproduction is authorised provided the source is acknowledged Printed in Italy 2 EXECUTIVE SUMMARY Polyvinylchloride (PVC) has been a very common material for the production of toys. It generally is manufactured with an addition of additives such as plasticisers to improve its functionality and facilitate its production process. PVC that can contain up to 50% by weight of plasticisers (Simoneau et al., 2001). Among plasticisers, 90% of the most commonly used to soften polymers for toys production are constituted by phthalates, such as diisononyl phthalate (DINP). The purpose of this study was to investigate the influence of the relative concentration of percentage of phthalates and nature of phthalates on their release in standard conditions. To obtain a suitable but rapid method of analysis, experiments were performed to study the effects on the modification of a standard operation procedure (SOP) previously validated at the EU level by JRC Ispra. A single extraction with a sufficient large volume of cyclohexane thus could be used instead of two extractions with a smaller volume of cyclohexane and resulted in more rapid yet reliable method. The final method is described in Annex 1 of this report. Samples of soft PVC were industrially produced especially for this study. Standard PVC disks with various percentages of di-isononyl phthalate (DINP), di- isodecyl phthalate (DIDP), di-ethyl-hexyll phthalate (DEHP), benzylbutyl phthalate (BBP) dibutylphthalate (DBP) or a binary mixture DINP/DBP in various proportions were prepared. 30 different types of disk were produced and tested. The disks were analysed for contents, homogeneity and sets were subjected to migration experiments of the various phthalates under dynamic conditions using the previously validated SOP with some modifications. The release from samples with a systematic manufacturing process and containing different phthalates at different concentrations showed correlations to their concentrations. Since previous studies using commercial toys had no showed such specific trends, these results suggest that the production process of toys may be an important issue with respect to release properties. The release of DEHP BBP and DBP tended to show a more linear correlation to the concentration, whereas for DINP, DIDP, DEHP and release the plasticiser showed non linear tendencies and saturation of release for high formulation contents. 3 Table of contents GLOSSARY ........................................................................................................................................5 SCOPE.................................................................................................................................................6 MATERIALS AND METHODS .......................................................................................................7 SAMPLES...........................................................................................................................................7 HOMOGENEITY TESTING STUDY ........................................................................................................9 Sampling......................................................................................................................................9 Analysis – extraction-identification -quantification..................................................................10 Determination of weight and thickness .....................................................................................12 MIGRATION METHODOLOGY AND STANDARD OPERATING PROCEDURE (SOP) FOR EXTRACTION IDENTIFICATION AND QUANTIFICATION OF THE RELEASED PHTHALATES ........................................12 Migration experiments ..............................................................................................................13 Extraction and quantification from the saliva simulant ............................................................14 RESULTS..........................................................................................................................................17 HOMOGENEITY OF TEST MATERIALS ...............................................................................................17 RELEASE OF PHTHALATES FROM PVC MATERIALS..........................................................................19 CONCLUSIONS...............................................................................................................................26 4 GLOSSARY DINP: di-isononyl phthalate DIDP: di-isodecyl phthalate DEHP: di-ethyl-hexyll phthalate BBP: benzylbutyl phthalate HPLC: high performance liquid chromatography GC-MS: gas chromatography mass spectrometry SIM: Single ion monitoring SOP: Standard operating procedure 5 SCOPE Systematic approaches to examine the migration behaviour of the above mentioned phthalates and their mixtures is not known. In order to obtain data on the release behaviour of relevant phthalates, the JRC initiated a study to 1) establish the suitability of existing in vitro methods for the determination of the release of phthalates 2) investigate the effect of the nature of the phthalate on their release in saliva simulant under foreseen human conditions, and 3) investigate the effect of the percentage of different phthalates in PVC materials on their release in saliva simulant. Thus the study was aimed to provide insight into the relation of phthalate concentration and nature versus release. The results are now reported in the context of the Chem-Test project on behalf of DG SANCO. 6 MATERIALS AND METHODS Samples Based on the requirements of the project, test samples were requested for production by the industry. Sheets made to specific technical specifications were produced by industry. The European Council for Plasticisers and Intermediates (ECPI) and Toys Industries of Europe (TIE) as well as their members provided chemical standards, and PVC materials necessary to the manufacture of the test samples. The samples were manufactured at Solvay. PVC samples were manufactured into especially prepared disks with either individual phthalates or binary mixtures of phthalates; The samples were produced as strips to be punched as disks for sampling purposes. The strips produced also represented increasing concentrations of phthalates or mixtures of phthalates. The study included DINP DIDP. DEHP, BBP, and DBP. The investigation was applied to various concentrations of the phthalates. The results were also compared again to a standard reference strip reproducing the one used in the validation test at EU level conducted successfully in 2001. The disks were made according to the formulation and manufacture used in the in- vivo study led by the Dutch Consensus Group (CCG) in 1998. PVC standard material was processed in sheets or strips, which could then be punched into disks with a specifically designed press prior to experiments. 7 The industrial descriptions of the samples are summarised in table 1 below (the full descriptions are reported in Annex); as the disks were produced sequentially, the samples codes represent respectively the disks produced in a first phase (phase 1, numbers 1 to 13) and second phase (phase 2, numbers 2.1 to 2.8). For all disks the common characteristics were the production process, as well as the remaining additives and components, where the only variating component was the nature and or the percentage of the phthalates (expressed in %). All disks had a diameter of 2.3 cm (punched), thickness of 3mm, and weight ca 12g. The base composition was 100 Phr of PVC, 3 Phr of Epoxidised Soybean Oil (ESBO), and 3 Phr of Ca-Zn. Strips produced with a binary mixture of DINP and DBP were made to have a ration of 4 for the proportions of DINP:DBP (based on the Phr). intended Conc. Sample code phthalate (%) Strip 1 DINP 15.20 Strip 2 DINP 24.80 Strip REF DINP